Process of stabilizing organic materials and product of said process



Pmmd Aug. 31, 1948 PROCESS OF STABXLIZING ORGANIC MATE- BILLS AND PRODUCT F SAID PROCESS Harry M. Barnes, Florham Park, N. J., assignor to General Foods Corporation, Hoboken, N. J., a corporation of Delaware No Drawing. Original application October 17,

1944, Serial No. 559,135. Divided and this appiication November 21, 1947, Serial No. 787,482

11 Claims. 1

The present invention relates to the stabilization of organic materials subject to oxidative deterioration. This application is a division of my application Serial No, 559,135 filed October 2 oxidation, it is advantageous to make use of. an anti-oxidant that is readily and substantially oil-soluble. This is especially true of foodstuffs containing oils in dispersion inasmuch as an anti- 1.7, 1944. 5 oxidant dissolved in the oil-will be at the locus An object of the inventionistoprovideaprocess of oxidation. B-pentadecyl resorcinol fulfills the for stabilizing organic materialssuch as certain condition of oil-solubility and is furthermore in- .essential oilsyanimaland vegetable oils and fats, soluble in water, so that itremains in the oil at cereals and other foodstutls containing such oils all times. or fats. against oxidative deterioration. The 5-pentadecyi resorcinol as such, or in ad- Another object o! the invention is to provide mixture with other substances may be applied to novel compositions of organic materials subject the material to I 't in y Suitable to oxidative deterioration and a compound which manne f t is desired to protect n 011 or t. is effective to stabilize the organic materials the anti-oxidant y ply be Stirred n a d against said deterioration. I allowed to dissolve. The S-pentadecyl resorcinol These and other objects will be more readily understood from the following specific description.

It, is well known that certain essential oils, vegetable and animal oilsand fats, cereals and other .foodstufis containing these oils'and fats undergo certain chemical changes when exposed to air or other oxidative influences, resulting in changes of color, odor, or other properties which render them objectionable or unusable.

I According to this invention, Ihave' found 'that' these organic materials subject to oxidative deterioration can be stabilized by the-addition of very small amounts of 5-pentadecyl resorcinol,

HO CiuHai This compound is a tasteless, .white crystalline solid melting at 92C. It is insoluble in water but readilysoiuble in oils, fats, hydrocarbons and organic solvents .in..general.

5-pentadecyl resorcinol was fed to rats a levels of 0.5% and'1.0%"of their=total diet by premixingit with a standard diet. At the end of two weeks, the animals receiving 5-pentadecyl resorcinol had gained somewhat less in body weight may be dusted upon the surface of materials such as meat products or incorporated by mechanical mixing into substantially dry and granular oil or fat-containing materials such as cereals, or it may be dissolved in an oil or fat carrier and the admixture stirred in or sprayed upon the material to be protected.

The concentrations of 5-pentadecyl'resorcinol necessary will depend upon the material. to which it is added and the length of time during which anti-oxidative protection is desired. In general, I have found that satisfactory results are obtained using concentrations ranging from 0.01 to 0.50%. i I

By the term animal .and vegetable oils and fats, Imean those oils and fats which are of animal or vegetable origin and are glycerides of the more or less unsaturated higher fatty acids mixed with some saturated glycerides. Some of these materials are fish oi-ls, lard, beef tallow, olive oil, coconut oil, and peanut oil. By essential oils I mean those volatile oils of characteristic odor derived from plants, leaves, flowers,

.fruits, etc. such as oil of bitter almonds and lemon oil.

Further embodiments of, my invention will appear from the more detailed description set forth below, it being understood however, that this more detaileddescription is given by way of illustration and explanation only, and not byway of limitation, since various changes therein may be made by those skilled in the art without departing from the scope and spirit of the present invention.

EXAMPLET Samples of a food product composed of wheattaining no S-pentadecyl resorcinol was similarly prepared. The samples were tested periodically for the onset for rancidity. Results of the tests follow.

Tun: I

Per cent of b-pentadecyl resorcinol reg figggg igf gacttive to food prodto develop Per cent Day: 0.00 17 0. 20 76 EXAMPLE II Tum: 11

Per cent of S-pentadecyl resorcinol reg lggggfig have to food prodto develop Per cent Day;

EXAll-[PLE III Samples of pulverized corn grits were prepared containing 0.20% and :02% -pentadecyl resorcinol. With each sample was mixed 9. material known to facilitate rancidity development in the corn grits. The resulting mixtures were placed in screw-cap glass jars and incubated at 113 F. A control sample containing no antioxidant was similarly prepared and treated. The results appear in the following table.

TABLE III Per cent of 5-penta- Time required decyl resoreinol reior rancidity lative to corn grits to develop Per cent Dora 0. 00 Less than 1 0.02 6 0. 48

EXAMPLE IV Samples of processed corn flour were similarly treated and tested as in Example 111. The results follow:

TABLE IV Per cent of t-penta- Time required decyl resorcinol refor rancidity lative to corn flour to develop Per cent Days The results shown in Examples 1, II, III and resorcinol as an anti-oxidant when added in small quantities to oil-containing vegetable products. 1

EXAMPLE V Batches of a aqueous solution of gelatin were homogenized with approximately 10% of oil of bitter almonds, to which varying amounts of 5-pentadecyl resorcinol were added. The resulting mixture was poured into trays in a layer about one-quarter inch thick, and dried rapidly to minimize oxidation. The dried product was cut into slabs, pulverized to 40-80 mesh, placed in wide-mouthed open bottles and stored at 100 F. for three weeks. A control sample without 5--pentadecyl resorcinol was similarly prepared. The amounts of oil of bitter almonds remaining after the drying and grinding process and after the three weeks storage period were determined. The following table records the results.

Lemond oil was mixed with gelatin and treated substantially as in Example V. The followin table records the percentage of lemon oil remaining after the drying and grinding process and after three weeks storage at 100 F.

Tun: VI

Per cent of lemon oil Per cent of opentammmmng delcyl resoil'cinol re ative to emon oil After drying ggg g and grinding 100 Per cent Per cent Per cent It is evident from the results recorded in Tables V and VI that'the losses sustained by oxidative deterioration of flavoring materials during processing and storage may be markedly decreased by the use of small quantities of 5-pentadecyl resorcinol.

EXAMPLE VII A sample of lard was stabilized by dissolving therein 0.20% 5-pentadecyl resorcinol by weight. The efl'ectiveness o! the 5-pentadecyl resorcinol as an oxidation inhibitor was measured in an accelerated oxidation test at 90 C. in a Barcroft- Warburg oxygen absorption apparatus. As a control an untreated. portion of the same lard was similarly tested. The induction period" reported in the table is the elapsed time from the start of the oxidation test until evidence 01 ran- IV clearly indicate the eflicacy of 5-pentad yl (6 cidity was observed.

TmIVII Induction periods and protection factors at 90 C. for S-pentadecfl resorcinol in lard Concentration Antioxidant Anti-oxidant Period Factor Per cent b-pentadecyl resorcinc-L none 2.

Induction period oi treated i'at Induction period of control EXAMPLE VIII 1 Protection Factor .was held in vacuo at room temperature for 16 hours while the remainder was toasted minutes at 150 C. in an electric oven. Samples of the evacuated material and of the toasted material (adjusted to 3.5% moisture) were incubated at 45 C. and observed over a period of time for evidence of rancidity. A control sample prepared with the same amount of added coconut oil but no S-pentadecyl resorcinol was treated in the same way and observed for rancidity.

The results of the observations are set out in the following table.

Tun VIII Anti-oxidant cooked into dough Days to go Rancid at 45 C.

Untoasted, 16 hrs. in Vacuo at Room Temperature Toasted and Ad listed to 3.5 a Moisture Anti-oxidant 0.05% 5-pentadecyl resorcinol 54 Control 27 It will be apparent from the foregoing that the invention is capable of many other variations, particularly with respect to the organic materials which are stabilized and the manner of incorporating the fi-pentadecyl resorcinol in the materials, without departing from the essential features of the invention.

Induction Protec i n I claim:

' 1. A process for stabilizing a material containing an essential oil against oxidative deterioration, which comprises adding thereto a small eil'ective amount of 5-pentadecyl resorcinol.

' 2. A process for stabilizing a material containing an essential oil against oxidative deterioration, which comprises adding thereto 5-pentadecyl resorcinol in a quantity of about 0.01% and about 0.50% by weight of said material.

3. A process for stabilizing a gelatin ioodstufl containing an essential oil subject to oxidative deterioration, which comprises incorporating in said foodstufi a small effective amount of 5-pentadecyl resorcinol as a stabilizer.

4. The process of claim 3 wherein the 5-pentadecyl resorcinol is incorporated in a quantity between about 0.01% and about 0.50% by weight of said gelatin ioodstufl.

5. A process for stabilizing an essential oil against oxidative deterioration. which comprises incorporating therein a small effective amount of 5-pentadecyl resorcinol.

6. A composition stabilized against oxidative deterioration comprising a material containing an essential oil subject to oxidative deterioration and a small amount of 5-pentadecyl resorcinol present in said material as a stabilizer.

7. A composition stabilized against oxidative deterioration comprising a material containing an essential oil subject to oxidative deterioration and from about 0.01% to about 0.50% by weight of 5-pentadecyl resorcinol present in said material asastabilizer.

8. A composition stabilized against oxidative deterioration comprising a gelatin foodstuff containing an essential oil subject to oxidative deterioration and a small amount of S-pentadecyl resorcinol present in said foodstufl as a stabilizer.

9. A composition stabilized against oxidative deterioration comprising a gelatin foodstufl' containing an essential oil subject to oxldative deterioration and from about 0.01% to about 0.50% by weight of S-pentadecyl resorcinol present in said foodstuff as a stabilizer,

10. A composition stabilized against oxidative deterioration comprising an essential oil subject to oxidative deterioration and a small quantity of 5-pentadecyl resorcinol present therein as a stabilizer.

11. A composition stabilized against oxidative deterioration comprising an essential all subject to oxidative deterioration and from about 0.01%

to about 0.50% by weight of 5-pentadecyl resorcinol present therein as a stabilizer.

HARRY M. BARNES. 

